CN106316795A - Method for preparing difluoroethanol through catalytic hydrogenation - Google Patents
Method for preparing difluoroethanol through catalytic hydrogenation Download PDFInfo
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- CN106316795A CN106316795A CN201610450896.2A CN201610450896A CN106316795A CN 106316795 A CN106316795 A CN 106316795A CN 201610450896 A CN201610450896 A CN 201610450896A CN 106316795 A CN106316795 A CN 106316795A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/58—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of halogen, e.g. by hydrogenolysis, splitting-off
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Abstract
The invention provides a method for preparing difluoroethanol through catalytic hydrogenation. The method has the beneficial effects that hydrogenation reduction reaction is carried out by using ethyl chlorodifluoroacetate as the raw material, a Pd/C as a catalyst, triethylanmine as an acid-binding agent and ethanol as a solvent; the atom F has higher electronegativity and HF can not be generated in the ethyl chlorodifluoroacetate hydrogenation process, but the C-Cl bond is easy to hydrogenate and HCl is easy to generate, thus neutralizing generated HCl by adding the acid-binding agent triethylanmine, propelling reaction to be carried out positively and increasing the conversion rate of ethyl chlorodifluoroacetate; on the other side, used in ester hydrogenation reaction, the Pd/C catalyst has good characteristics of low hydrogen-ester ratio, high raw material conversion rate, high alcohol selectivity, stable catalyst, and the like; and therefore, the method has the effect of solving the problems that the reaction process in the traditional ester hydrogenation process is complex, is high in investment and is not suitable for small-scale production in the fine chemical industry field.
Description
Technical field
The present invention relates to technical field of catalytic chemistry, particularly relate to a kind of method that catalytic hydrogenation prepares difluoroethanol.
Background technology
Fluorinated alcohols and fluoroester belong to aliphatic fluoro-containing intermediate, at field tools such as pesticide, medicine synthesis, material, dyestuffs
There is the best DEVELOPMENT PROSPECT, there is high added value, be important organic synthesis intermediate.At present, it has been suggested that synthesis two
The multiple method of fluoroethanol, can be by especially with hydride reduction difluoroacetic acid chloride [AL.Henne and RL.Pelley-
JACS, 74 (1952), 1426-8] or reduced [Asahi Chemical, the patent of 24/05/85 by catalytic hydrogenation
JP61268639] or by with sodium borohydride reduction ethyl difluoro [M.Lewis and E.deClerck-J Chem
Res., Miniprint 8 (2001), 844-56] prepare difluoroethanol.
Industrial general employing carboxylate catalytic hydrogenation prepares fluorinated alcohols and fluoroester, catalyst be mainly nickel, chromium, copper,
The transition metal such as manganese.Wherein, Cu catalyst is the catalyst that current commercial Application most widely prepares difluoroethanol, but, Cu
There is the biggest gap at hydrogenation activity, selectivity, hydrogen ester than aspect in catalyst, it is difficult to adapts to raw materials quality in actual industrial production
The often requirement of fluctuation.Therefore, hydrogenation catalyst need to have low hydrogen ester ratio, preferably activity and selectivity, thus extends catalysis
Agent service life.On the other hand, preparing difluoroethanol and use tradition ester through hydrogenation fixed-bed process flow process, it operates complexity, equipment
Relatively costly, investment is big, and can not effectively reclaim catalyst, is not suitable for field of fine chemical small-scale production.
It is considered as desirable by the inventor to, it is provided that a kind of catalytic hydrogenation prepares the method for difluoroethanol, utilize slurry bed system ester through hydrogenation to react,
Improve conversion ratio and the selectivity of reaction, thus improve the economic benefit in commercial production.
Summary of the invention
The technical problem to be solved in the present invention is a kind of method providing catalytic hydrogenation to prepare difluoroethanol, technique letter
Single, feed stock conversion is high.
In view of this, the invention provides a kind of method that catalytic hydrogenation prepares difluoroethanol, comprise the following steps: step
A) Pd/C, difluoro ethyl chloroacetate, ethanol and triethylamine are poured in reactor successively, tighten kettle cover；Step b) to described instead
Answer and still is filled with H2And check whether gas leakage；Described reactor is heated to 90-200 DEG C in silicone oil bath by step c), during reaction
Between be 5-30h, prepare difluoroethanol.
Preferably, the mass ratio of described Pd/C, difluoro ethyl chloroacetate, ethanol and triethylamine is 0.1-1:3-10:10-
30:1-3.
Preferably, the mass ratio of described Pd/C, difluoro ethyl chloroacetate, ethanol and triethylamine is 0.5-1:5-10:15-
30:1.4-2.8.
Preferably, tightening kettle cover described in makes reactor be in air-tight state.
Preferably, in step b, in described reactor, it is filled with the H of 3-5MPa2And check whether gas leakage.
Preferably, in step b, in described reactor, it is filled with the H of 4-5MPa2And check whether gas leakage.
Preferably, described step b is particularly as follows: be filled with H in described reactor2Check whether gas leakage, air tight then hydrogen
Gas is released, and in triplicate, is the most again flushed with hydrogen gas.
Preferably, in step c, reaction is carried out under magnetic stirring.
Preferably, described step c particularly as follows: described reactor is heated to 90-200 DEG C in silicone oil bath, the response time
For 5-30h, after having reacted, it is cooled to room temperature, opens vent valve venting, then turn on kettle cover, be dried to clean with dropper sampling
In sample bottle, carry out chromatography.
Preferably, described reactor is heated to 150-200 DEG C in silicone oil bath.
The invention provides a kind of method that catalytic hydrogenation prepares difluoroethanol, comprise the following steps: by Pd/C, difluoro chlorine
Ethyl acetate, ethanol and triethylamine are poured in reactor successively, tighten kettle cover；It is filled with H in described reactor2And check whether
Gas leakage；Described reactor is heated in silicone oil bath 90-200 DEG C, and the response time is 5-30h, obtains difluoroethanol.With existing
Technology is compared, the present invention with difluoro ethyl chloroacetate as raw material, Pd/C as catalyst, triethylamine as acid binding agent, ethanol is as solvent
Carry out hydrogenation reduction.Owing in difluoro ethyl chloroacetate hydrogenation process, F atom has bigger electronegativity, it is impossible to generate HF,
But C-Cl key is easily hydrogenated with, easily generates HCl, thus the present invention is by the HCl adding in acid binding agent triethylamine and generate, advance anti-
Should carry out to forward, improve the conversion ratio of difluoro ethyl chloroacetate.On the other hand, Pd/C catalyst is used in ester through hydrogenation reaction,
Have hydrogen ester than low, feed stock conversion is high, alcohol selectivity is high and the good characteristics such as catalyst stabilization.Therefore, the present invention solves
Traditional ester through hydrogenation process reaction complex process, investment are big, are not suitable for the problems such as field of fine chemical small-scale production.
Detailed description of the invention
In order to be further appreciated by the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but
Should be appreciated that these describe simply as to further illustrate the features and advantages of the present invention rather than to the claims in the present invention
Limit.
The embodiment of the invention discloses a kind of method that catalytic hydrogenation prepares difluoroethanol, comprise the following steps: step a)
Pd/C, difluoro ethyl chloroacetate, ethanol and triethylamine are poured in reactor successively, tightens kettle cover；Step b) is to described reaction
Still is filled with H2And check whether gas leakage；Described reactor is heated to 90-200 DEG C in silicone oil bath by step c), the response time
For 5-30h, obtain difluoroethanol.
The present invention uses slurry bed system liquid phase reactor technique, uses Pd/C catalyst, simplifies workflow, improves reaction
Conversion ratio, also solving noble metal catalyst in fixed bed is difficult to the problem reclaimed simultaneously, and then reduces production cost, existing
For Chemical Manufacture has certain reference significance.
Preferably, the mass ratio of described Pd/C, difluoro ethyl chloroacetate, ethanol and triethylamine is 0.1-1:3-
10:10-30:1-3, more preferably 0.5-1:5-10:15-30:1.4-2.8.
Wherein, the present invention is with triethylamine as acid binding agent.In difluoro ethyl chloroacetate hydrogenation process, just have relatively due to F atom
Big electronegativity, C-F key is stronger, it is impossible to generate HF.But C-Cl key is easily hydrogenated with, generates HCl, HCl and there is highly acid, perishable
Erosion equipment.Therefore, the present invention is by the HCl adding in acid binding agent triethylamine and generate, and meanwhile, reaction can be advanced to enter to forward
OK, the conversion ratio of difluoro ethyl chloroacetate is improved.Course of reaction is as follows:
Preferably, in step a, the present invention makes reactor be in air-tight state by tightening kettle cover, otherwise can leak
Gas, and then affect being smoothed out of reaction.
Preferably, in step b, the present invention is filled with the H of 3-5MPa in described reactor2And check whether Lou
Gas, is more preferably filled with the H of 4-5MPa2.Described step b is particularly as follows: be filled with H in described reactor2Check whether gas leakage, do not leak
Gas is then released hydrogen, in triplicate, is the most again flushed with hydrogen gas.
Preferably, in step c, reaction is carried out under magnetic stirring.Described step c is particularly as follows: by described reaction
Still is heated to 90-200 DEG C in silicone oil bath, and the response time is 5-30h, is cooled to room temperature after having reacted, and opens vent valve and puts
Gas, then turn on kettle cover, with in dropper sampling to the clean sample bottle being dried, carry out chromatography.Preferably, by described reactor
150-200 DEG C it is heated in silicone oil bath, more preferably 180-200 DEG C.Wherein, the present invention to exit after it cools down again, if
When temperature is the highest, just venting will make the liquid in reactor together erupt with gas.
From above scheme it can be seen that the present invention provides a kind of slurry bed system ester through hydrogenation reaction, Pd/C catalyst is used for ester
In hydrogenation reaction, have hydrogen ester than low, feed stock conversion is high, alcohol selectivity is high and the good characteristics such as catalyst stabilization.Secondly,
The present invention uses reactor technological process to replace tradition ester through hydrogenation fixed-bed process flow process, simplifies operating process, reduces and set
Standby cost, and can effectively reclaim noble metal catalyst, exist during effectively solving traditional catalyst catalysis ester through hydrogenation
Hydrogen ester than problem too high, that feed stock conversion alcohol selectivity is low.Again, the present invention is simple to operate, is suitable for field of fine chemical
Small lot batch manufacture.
In order to be further appreciated by the present invention, the technical scheme provided the present invention below in conjunction with embodiment is carried out specifically
Bright, protection scope of the present invention is not limited by the following examples.
Raw material and chemical reagent that the embodiment of the present invention uses are commercial.
Embodiment 1
Take the reactor of a dried and clean, inwardly add Magnetitum.On pan paper, weigh 0.5gPd/C with electronic balance, use
Beaker weighs difluoro ethyl chloroacetate 10g, ethanol 30g, triethylamine 2.8g, is sequentially added into reactor, tightens reaction kettle cover.
It is filled with whether 4MPa hydrogen instrument testing still leaks gas, does not leaks, exit, continue in triplicate, be inflated to for the last time
1.0MPa.Put in the silicone oil bath of 150 DEG C reaction 24h, after the time arrives, take out being cooled to temperature and drop to less than 60 DEG C, venting, twist
Opening reaction kettle cover, sample with dropper, carry out chromatography, result is as shown in table 1.
Embodiment 2
Take the reactor of a dried and clean, inwardly add Magnetitum.On pan paper, weigh 0.5gPd/C with electronic balance, use
Beaker weighs difluoro ethyl chloroacetate 5g, ethanol 15g, triethylamine 1.4g, is sequentially added into reactor, tightens reaction kettle cover.
It is filled with whether 4MPa hydrogen instrument testing still leaks gas, does not leaks, exit, continue in triplicate, be inflated to for the last time
0.5MPa.Put in the silicone oil bath of 180 DEG C reaction 5h, after the time arrives, take out being cooled to temperature and drop to less than 60 DEG C, venting, twist
Opening reaction kettle cover, sample with dropper, carry out chromatography, result is as shown in table 1.
Embodiment 3
Take the reactor of a dried and clean, inwardly add Magnetitum.On pan paper, weigh 0.5gPd/C with electronic balance, use
Beaker weighs difluoro ethyl chloroacetate 10g, ethanol 30g, triethylamine 2.8g, is sequentially added into reactor, tightens reaction kettle cover.
It is filled with whether 4MPa hydrogen instrument testing still leaks gas, does not leaks, exit, continue in triplicate, be inflated to 1MPa for the last time.
Put in the silicone oil bath of 180 DEG C reaction 24h, after the time arrives, take out being cooled to temperature and drop to less than 60 DEG C, venting, turn on reaction
Kettle cover, samples with dropper, carries out chromatography, and result is as shown in table 1.
Embodiment 4
Take the reactor of a dried and clean, inwardly add Magnetitum.On pan paper, weigh 0.5gPd/C with electronic balance, use
Beaker weighs difluoro ethyl chloroacetate 10g, ethanol 30g, triethylamine 2.8g, is sequentially added into reactor, tightens reaction kettle cover.
It is filled with whether 4MPa hydrogen instrument testing still leaks gas, does not leaks, exit, continue in triplicate, be inflated to for the last time
1.0MPa.Put in the silicone oil bath of 200 DEG C reaction 30h, after the time arrives, take out being cooled to temperature and drop to less than 60 DEG C, venting, twist
Opening reaction kettle cover, sample with dropper, carry out chromatography, result is as shown in table 1.
Comparative example 1
Take the reactor of a dried and clean, add Magnetitum.On pan paper, 0.1-1gPd/C is weighed with electronic balance.By burning
Cup weighs ethanol 30g, difluoro ethyl chloroacetate 10g, triethylamine 2.8g respectively, is sequentially added into reactor, tightens reactor
Lid.It is filled with 4MPa hydrogen and whether leaks gas with instrument testing still, not leaking, exit, continuing in triplicate, be inflated to for the last time
1.0MPa.It is then placed in the silicone oil bath of 45 DEG C reacting 5h, after the time, takes out being cooled to temperature and drop to about 40 DEG C, venting,
Turning on reaction kettle cover, sample with dropper, carry out chromatography, result is as shown in table 1.
Comparative example 2
Take the reactor of a dried and clean, inwardly add Magnetitum.On pan paper, weigh 0.5gPd/C with electronic balance, use
Beaker weighs difluoro ethyl chloroacetate 5g, ethanol 15g, triethylamine 1.4g, is sequentially added into reactor, tightens reaction kettle cover.
It is filled with whether 4MPa hydrogen instrument testing still leaks gas, does not leaks, exit, continue in triplicate, be inflated to for the last time
0.5MPa.Put in the silicone oil bath of 90 DEG C reaction 5h, after the time arrives, take out being cooled to temperature and drop to less than 60 DEG C, venting, turn on
Reaction kettle cover, samples with dropper, carries out chromatography, and result is as shown in table 1.
Comparative example 3
Take the reactor of a dried and clean, inwardly add Magnetitum.On pan paper, weigh 0.5gPd/C with electronic balance, use
Beaker weighs difluoro ethyl chloroacetate 5g, ethanol 15g, triethylamine 1.4g, is sequentially added into reactor, tightens reaction kettle cover.
It is filled with whether 4MPa hydrogen instrument testing still leaks gas, does not leaks, exit, continue in triplicate, be inflated to for the last time
1.0MPa.Put in the silicone oil bath of 90 DEG C reaction 5h, after the time arrives, take out being cooled to temperature and drop to less than 60 DEG C, venting, turn on
Reaction kettle cover, samples with dropper, carries out chromatography, and result is as shown in table 1.
Raw material that table 1 embodiment of the present invention and comparative example use and product
The explanation of above example is only intended to help to understand method and the core concept thereof of the present invention.It is right to it should be pointed out that,
For those skilled in the art, under the premise without departing from the principles of the invention, it is also possible to the present invention is carried out
Some improvement and modification, these improve and modify in the protection domain also falling into the claims in the present invention.
Claims (10)
1. the method that a catalytic hydrogenation prepares difluoroethanol, it is characterised in that comprise the following steps:
Pd/C, difluoro ethyl chloroacetate, ethanol and triethylamine are poured in reactor by step a) successively, tighten kettle cover；
Step b) is filled with H in described reactor2And check whether gas leakage；
Described reactor is heated to 90-200 DEG C in silicone oil bath by step c), and the response time is 5-30h, obtains difluoroethanol.
Method the most according to claim 1, it is characterised in that described Pd/C, difluoro ethyl chloroacetate, ethanol and triethylamine
Mass ratio be 0.1-1:3-10:10-30:1-3.
Method the most according to claim 2, it is characterised in that described Pd/C, difluoro ethyl chloroacetate, ethanol and triethylamine
Mass ratio be 0.5-1:5-10:15-30:1.4-2.8.
Method the most according to claim 1, it is characterised in that described in tighten kettle cover and make reactor be in air-tight state.
Method the most according to claim 1, it is characterised in that in step b, is filled with the H of 3-5MPa in described reactor2
And check whether gas leakage.
Preparation method the most according to claim 5, it is characterised in that in step b, is filled with 4-5MPa in described reactor
H2And check whether gas leakage.
Preparation method the most according to claim 1, it is characterised in that described step b particularly as follows:
It is filled with H in described reactor2Check whether gas leakage, air tight, hydrogen is released, in triplicate, is the most again flushed with hydrogen
Gas.
8., according to the preparation method described in claim 1-7 any one, it is characterised in that in step c, reaction is in magnetic agitation
Under carry out.
9. according to the preparation method described in claim 1-7 any one, it is characterised in that described step c particularly as follows:
Described reactor is heated in silicone oil bath 90-200 DEG C, and the response time is 5-30h, is cooled to room after having reacted
Temperature, opens vent valve venting, then turns on kettle cover, with in dropper sampling to the clean sample bottle being dried, carries out chromatography.
10. according to the preparation method described in claim 1-7 any one, it is characterised in that by described reactor at silicone oil bath
In be heated to 150-200 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610450896.2A CN106316795A (en) | 2016-06-21 | 2016-06-21 | Method for preparing difluoroethanol through catalytic hydrogenation |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610450896.2A CN106316795A (en) | 2016-06-21 | 2016-06-21 | Method for preparing difluoroethanol through catalytic hydrogenation |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108003026A (en) * | 2016-10-28 | 2018-05-08 | 南通宝凯化工有限公司 | A kind of preparation process of ethyl difluoro |
| CN108503507A (en) * | 2018-02-08 | 2018-09-07 | 南通宝凯化工有限公司 | A kind of production technology of difluoroethanol |
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| WO2007093567A1 (en) * | 2006-02-13 | 2007-08-23 | Solvay (Societe Anonyme) | Process for the manufacture of fluorinated alcohols |
| CN101687740A (en) * | 2007-09-18 | 2010-03-31 | 中央硝子株式会社 | Processes for production of 2-bromo-2,2-difluoroethanol and 2-(alkylcarbonyloxy)-1,1-difluoroethanesulfonic acid salt |
| CN102553614A (en) * | 2011-12-26 | 2012-07-11 | 浙江师范大学 | Catalyst for producing difluoroethanol by hydrogenation of difluoro carboxylate and preparation method thereof |
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2016
- 2016-06-21 CN CN201610450896.2A patent/CN106316795A/en active Pending
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| US5455376A (en) * | 1993-12-10 | 1995-10-03 | Bayer Aktiengesellschaft | Process for the preparation of aliphatic omega-difluorocarboxyl compounds |
| WO2007093567A1 (en) * | 2006-02-13 | 2007-08-23 | Solvay (Societe Anonyme) | Process for the manufacture of fluorinated alcohols |
| CN101687740A (en) * | 2007-09-18 | 2010-03-31 | 中央硝子株式会社 | Processes for production of 2-bromo-2,2-difluoroethanol and 2-(alkylcarbonyloxy)-1,1-difluoroethanesulfonic acid salt |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108003026A (en) * | 2016-10-28 | 2018-05-08 | 南通宝凯化工有限公司 | A kind of preparation process of ethyl difluoro |
| CN108503507A (en) * | 2018-02-08 | 2018-09-07 | 南通宝凯化工有限公司 | A kind of production technology of difluoroethanol |
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